WO2007110611A1 - Materiau composite - Google Patents

Materiau composite Download PDF

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Publication number
WO2007110611A1
WO2007110611A1 PCT/GB2007/001067 GB2007001067W WO2007110611A1 WO 2007110611 A1 WO2007110611 A1 WO 2007110611A1 GB 2007001067 W GB2007001067 W GB 2007001067W WO 2007110611 A1 WO2007110611 A1 WO 2007110611A1
Authority
WO
WIPO (PCT)
Prior art keywords
composite material
material according
carbonate
unoriented
inorganic filler
Prior art date
Application number
PCT/GB2007/001067
Other languages
English (en)
Inventor
Malcolm Brown
Ben Alcock
Michael Andrew Hall
De Oca Horacio Montes
Mark Bonner
Original Assignee
Smith & Nephew, Plc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Smith & Nephew, Plc filed Critical Smith & Nephew, Plc
Publication of WO2007110611A1 publication Critical patent/WO2007110611A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
    • A61L27/446—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with other specific inorganic fillers other than those covered by A61L27/443 or A61L27/46
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
    • A61L27/46—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with phosphorus-containing inorganic fillers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/12—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L31/125—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
    • A61L31/127—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix containing fillers of phosphorus-containing inorganic materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/12—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L31/125—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
    • A61L31/128—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix containing other specific inorganic fillers not covered by A61L31/126 or A61L31/127
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates

Definitions

  • the present invention relates to composite polymeric materials and methods for making the same.
  • the present invention relates to the orientation of highly filled polymeric materials resulting in improved mechanical properties such as tensile strength, ductility and strength retention.
  • Orthopaedic surgery involves the implantation of materials that must be both biocompatible and capable of bearing high loads.
  • metals such as titanium and titanium alloys have been used, but these suffer a number of disadvantages, for example they can cause stress shielding and require a second medical procedure to remove them from the body.
  • particulate fillers i.e. buffers, radiopaque agents, and osteoconductive agents etc
  • particulate fillers have been incorporated into medical devices to improve x-ray visibility, biocompatibility, strength retention profile and to facilitate bone replacement of polymeric implants.
  • the optimum buffering or osteoconductive properties of these polymeric composites are often achieved by incorporating filler in excess of 35 wt/wt%.
  • the incorporation of these fillers is known to have a detrimental effect on the mechanical properties (i.e. strength and ductility) of the final material.
  • mechanical properties i.e. strength and ductility
  • these materials would find applications in medium - high loading bearing applications if the polymer composites had sufficiently high strength & ductility. Improvements of the mechanical properties of particulate filled polymer composites have been achieved by orientating the material. However processing of these particulate composites has been only been achieved for composites containing filler at 20 wt% and below.
  • a composite material comprising amorphous polymer and 25-50% by weight inorganic filler where the composite material has been orientated to improve its mechanical properties.
  • a composite material comprising amorphous polymer and 25-50% by weight inorganic filler where the composite material has been orientated to a draw ratio of at least two.
  • Draw ratio can be defined as the final sample length divided by the initial sample length.
  • Amorphous polymer is defined herein to be any polymer with less than 10% crystallinity. Suitable polymers include resorbable and non-resorbable polymers.
  • non-resorbable polymers may be polystyrene, polymethyl methacrylate (PMMA), polybutylmethyl acrylate (PBMA) polyethyl methy acrylate (PEMA) and copolymers or blends thereof.
  • PMMA polymethyl methacrylate
  • PBMA polybutylmethyl acrylate
  • PEMA polyethyl methy acrylate
  • the resorbable polymers may be polylactide and copolymers thereof where the lactide component comprises at least 50% by weight; polyglycolide and copolymers thereof where the glycolide comprises at least 50% by weight and polydioxanone and copolymers thereof where the dioxanone comprises at least 50% by weight.
  • Other copolymer components may comprise lactide, glycolide, caprolactone, dioxanone, trimethylene carbonate or dimethyltrimethylene carbonate.
  • the amorphous polymer may also be a blend of two or more polymers.
  • the amorphous polymer may further comprise a non-buffering inorganic material such as hydroxyapatite.
  • the amorphous polymer may further comprise one or more bioactive agents that would promote tissue repair in the body, for example angiogenic agents, antimicrobial agents, osteoinductive agents or osteoconductive agents.
  • the inorganic fillers of the present invention may be buffers, radiopaque agents, and/or osteoconductive agents.
  • the inorganic fillers are typically particulates and may be crystalline particulates.
  • inorganic fillers that act as buffers improve strength retention of degradable systems by reacting with the acidic breakdown products of the amorphous polymer.
  • the inorganic filler comprises calcium, sodium, potassium, magnesium, barium, zirconium, bismuth, silver, gold, copper, zinc elements, compounds or any combination thereof.
  • the inorganic filler is a crystalline calcium, sodium, zirconium, bismuth, barium, silicon, tungsten or magnesium salt.
  • the inorganic filler is calcium carbonate, calcium hydrogen carbonate, calcium phosphate, dicalcium phosphate, tricalcium phosphate, magnesium carbonate, sodium carbonate, hydroxyapatite, bone, phosphate glass, silicate glass, magnesium phosphate, sodium phosphate, barium sulphate, barium carbonate, zirconium sulphate, zirconium carbonate, zirconium dioxide, bismuth trioxide, bismuth oxychloride, bismuth subcarbonate, tungsten oxide or any combination thereof.
  • the filler may be a particulate that can have a range of sizes and geometries.
  • the particulate shapes may be needles, cubes, platelets, fibres or spheres.
  • the filler particulates are shaped to enhance the mechanical properties of the composite material.
  • the particulate size is typically between lOnm and 1mm.
  • inorganic fillers that act as radiopaque agents are barium sulphate, barium carbonate, zirconium sulphate, zirconium carbonate, zirconium dioxide, bismuth trioxide, bismuth oxychloride, bismuth subcarbonate or tungsten oxide
  • the filler particulates may be pre-treated with a coupling agent such as a fatty acid, fatty acid anhydride or siloxane in order to enhance the properties of the composite.
  • a coupling agent such as a fatty acid, fatty acid anhydride or siloxane
  • inorganic fillers that act as osteogenic agents are calcium carbonate, calcium phosphate, dicalcium phosphate, tricalcium phosphate, hydroxyapatite, bone, phosphate glasses, silicate glasses, magnesium phosphate, sodium phosphate,
  • the unoriented composite material can be made by blending the inorganic filler into the amorphous polymer by, for example, solution casting methods, melt compounding methods or by in situ polymerizing the polymer around the inorganic filler.
  • orientation methods are suitable for creating the orientated composite material. These include both thermal , and solution methods. Suitable methods include die drawing, fibre drawing, oven drawing, zone drawing, zone annealing, ram extrusion, hydrostatic extrusion, rolling, gel spinning, shear controlled orientation in injection moulding, roll drawing, biaxial drawing and solid state extrusion. These orientation methods can be carried out under constant load or constant extension.
  • the orientated composite material may be at least 20% higher strength than the unoriented composite material. Preferably it has at around 50% higher strength than the unoriented composite material. Most preferably it has at least 100% higher strength than the unoriented composite material.
  • the orientated composite material may be at least 100% more ductile than the unoriented composite material, preferably it is at least 200% more ductile than the unoriented material.
  • the orientated composite material can be used to generate second generation composite, for example a fibre-reinforced composite, or further processed to generate a medical device, hi one embodiment the orientated composite material is forged or machined into a fixation plate, hi another embodiment the orientated composite material is forged or machined into a screw. Ih another embodiment the orientated composite material is forged or machined into a suture anchor. In another embodiment the orientated composite material is used as a bone graft substitute.
  • Example 1 Method for Production and Zone Drawing of Oriented Polymers Containing 35 w /w CaCO 3
  • Example 2 Method for Production and Die Drawing of Oriented Polymers Containing 357w CaCO ⁇
  • PDLGA poly(DL-lactide-co-glycolide)
  • This rod was drawn by pulling through a conical die (heated to 70 0 C) at a rate of lOmm-min "1 .
  • the rod experiences local deformation causing a drawing effect.
  • the tensile mechanical properties of 5 specimens of drawn and undrawn filled PDLGA rod and the results are shown in table 2.
  • Example 3 Method for Drawing and Production of Oriented Polymers Containing 35 w /w CaCO 3 and a Fatty Acid Anhydride
  • PDLGA poly(DL-lactide-co-glycolide)
  • 30Og of calcium carbonate was vacuum dried at 150 0 C, 10 mbar for 48 hours.
  • 4Og of dried CaCO 3 and 0.571g of Dodecenylsuccinic anhydride (DSA) were placed •together in 40ml CH 2 Cl 2 . The contents were thoroughly mixed and air dried for 72hours, followed by oven drying at 200 0 C for 5 minutes.
  • 96.75g of dried PDLGA was dry blended with 53.25g of dried DSA coated CaCO 3 , and fed into a twin screw extruder, operating at 225rpm and 200 0 C.
  • the output of the extruder was a lmm diameter PDLGA fibre containing dispersed DSA coated CaCO 3 particles. A 30cm length of this extruded.
  • PDLGA fibre was drawn by locally applying a non-contact "zone” heater and applying a constant extension of 0.5mm.min “1 to the fibre. The "zone” heater was moved along the fibre as the fibre was extended and local deformation occurred causing a drawing effect. The tensile mechanical properties of drawn PDLGA fibre are shown in table 3.
  • Example 4 Method for production and drawing of polymer fibres containing 50% w /w CaCO3
  • Example 5 Method for Production and Drawing of Non-Resorbable Polymer Fibres Containing 35% w /w CaCO3
  • Example 6 Method for Drawing and Production of Oriented Polymers Containing 35 w /w CaSQ 4.
  • a 30cm length of this extruded polymer fibre was drawn by locally applying a non-contact "zone” heater and applying a constant extension of 25mm.min “1 .
  • the "zone” heater is moved along the fibre as the fibre is extended and local deformation occurs causing a drawing effect.
  • the tensile mechanical properties of drawn and undrawn polymer fibre are shown in table 6.
  • Example 7 Zone drawing of PDLLA-co-DL f70/30) CaCO 1 f35%wAv)
  • Amorphous poly(D,L Lactide-co-DL) with 35% w/w CaCO 3 fibres lmm in diameter were prepared using a twin screw extruder. The fibres were drawn using the zone drawing technique. A fibre approximately 40cm long is attached at the top of the Zwick materials testing apparatus while the bottom end of the fibre is attached to a load (10Og). The fibre is passed through a local heater held at the draw temperature (7O 0 C) which moves upwards at lOmm/min while the fibre is drawn due to the hanged load. The tensile mechanical properties of drawn and undrawn polymer fibre are shown in table 7. [0054]

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Public Health (AREA)
  • Inorganic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Veterinary Medicine (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Vascular Medicine (AREA)
  • Dermatology (AREA)
  • Surgery (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Transplantation (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials For Medical Uses (AREA)

Abstract

L'invention concerne un matériau composite de grande résistance pour applications orthopédiques comprenant un polymère amorphe et de grandes quantités d'une matière de remplissage inorganique, le matériau ayant été fortement orienté de manière à accroître la résistance et le module du composite.
PCT/GB2007/001067 2006-03-24 2007-03-26 Materiau composite WO2007110611A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0605885A GB0605885D0 (en) 2006-03-24 2006-03-24 Composite Material
GB0605885.3 2006-03-24

Publications (1)

Publication Number Publication Date
WO2007110611A1 true WO2007110611A1 (fr) 2007-10-04

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Application Number Title Priority Date Filing Date
PCT/GB2007/001067 WO2007110611A1 (fr) 2006-03-24 2007-03-26 Materiau composite

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GB (1) GB0605885D0 (fr)
WO (1) WO2007110611A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8129477B1 (en) 2008-08-06 2012-03-06 Medtronic, Inc. Medical devices and methods including blends of biodegradable polymers
CN113018515A (zh) * 2021-03-04 2021-06-25 湖南华锐科技集团股份有限公司 一种可降解锌基合金骨骼固定系统材料及其制备方法
US11530313B2 (en) 2012-10-16 2022-12-20 Omya International Ag Process of controlled chemical reaction of a solid filler material surface and additives to produce a surface treated filler material product
US11708478B2 (en) * 2016-07-19 2023-07-25 Omya International Ag Use of mono-substituted succinic anhydride

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0510998A2 (fr) * 1991-04-26 1992-10-28 MITSUI TOATSU CHEMICALS, Inc. Film poreux
US6207792B1 (en) * 1992-10-02 2001-03-27 Cargill, Incorporated Melt-stable amorphous lactide polymer film and process for manufacture thereof
US20040127131A1 (en) * 2002-12-31 2004-07-01 Potnis Prasad Shrikirshna Breathable, extensible films made with two-component single resins
US20050112350A1 (en) * 2003-11-21 2005-05-26 Xin Ning Biodegradable and breathable polymer film

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0510998A2 (fr) * 1991-04-26 1992-10-28 MITSUI TOATSU CHEMICALS, Inc. Film poreux
US6207792B1 (en) * 1992-10-02 2001-03-27 Cargill, Incorporated Melt-stable amorphous lactide polymer film and process for manufacture thereof
US20040127131A1 (en) * 2002-12-31 2004-07-01 Potnis Prasad Shrikirshna Breathable, extensible films made with two-component single resins
US20050112350A1 (en) * 2003-11-21 2005-05-26 Xin Ning Biodegradable and breathable polymer film

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8129477B1 (en) 2008-08-06 2012-03-06 Medtronic, Inc. Medical devices and methods including blends of biodegradable polymers
US11530313B2 (en) 2012-10-16 2022-12-20 Omya International Ag Process of controlled chemical reaction of a solid filler material surface and additives to produce a surface treated filler material product
US11708478B2 (en) * 2016-07-19 2023-07-25 Omya International Ag Use of mono-substituted succinic anhydride
CN113018515A (zh) * 2021-03-04 2021-06-25 湖南华锐科技集团股份有限公司 一种可降解锌基合金骨骼固定系统材料及其制备方法
CN113018515B (zh) * 2021-03-04 2022-09-13 湖南华锐科技集团股份有限公司 一种可降解锌基合金骨骼固定系统材料及其制备方法

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Publication number Publication date
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